Synthesis and transformation of metallacycles 25.* On a mechanism of the Ni(acac)2-catalyzed converson of 3-alkyl-1-ethylalumacyclopentanes into 1,1-disubstituted cyclopropanes

Article abstract of DOI:10.1023/A:1012705711678

The reactions of 3-alkyl-1-ethylalumacyclopentanes with allyl halides in the presence of Ni(acac)₂ as a catalyst were studied by dynamic NMR spectroscopy. Under the action of Ni complexes, alumacyclopentanes initially undergo intramolecular hydride transfer to give but-3-enyl(ethyl)aluminum hydrides and then react with the starting allyl halide, yielding but-3-enyl(ethyl)aluminum halides. Subsequent intramolecular carboalumination affords the corresponding 1,1-disubstituted cyclopropanes.

Full text of DOI:10.1023/A:1012705711678

Russian Chemical Bulletin, International Edition, Vol. 50, No. 8, pp. 1465—1468, August, 2001
1465
Organometallic Chemistry
Synthesis and transformation of metallacycles
5.* On a mechanism of the Ni(acac) -catalyzed conversion
2
2
of 3-alkyl-1-ethylalumacyclopentanes into 1,1-disubstituted cyclopropanes
«
U. M. Dzhemilev, A. G. Ibragimov, L. O. Khafizova, L. V. Parfenova, D. F. Yalalova, and L. M. Khalilov
Institute of Petrochemistry and Catalysis, Bashkortostan Republic Academy of Sciences
and Ufa Research Center of the Russian Academy of Sciences,
1
41 prosp. Oktyabrya, 450075 Ufa, Russian Federation.
Fax: +7 (347 2) 31 2750. E-mail: ink@anrb.ru
The reactions of 3-alkyl-1-ethylalumacyclopentanes with allyl halides in the presence of
Ni(acac)2 as a catalyst were studied by dynamic NMR spectroscopy. Under the action of Ni
complexes, alumacyclopentanes initially undergo intramolecular hydride transfer to give
but-3-enyl(ethyl)aluminum hydrides and then react with the starting allyl halide, yielding
but-3-enyl(ethyl)aluminum halides. Subsequent intramolecular carboalumination affords the
corresponding 1,1-disubstituted cyclopropanes.
Key words: organoaluminum compounds, alumacyclopentanes, catalysis, olefins, allyl
halides, substituted cyclopropanes.
Previously,2 we showed that 3-alkyl-1-ethylaluma-
cyclopentanes (ACP) 1 obtained by the Cp ZrCl -cata-
Scheme 1
2
2
lyzed reactions of α-olefins with AlEt33 react with an
excess of allyl chloride in the presence of Ni(acac)2 to
give 1,1-disubstituted cyclopropanes. The resulting
R
[Zr]
Cl, [Ni]
–C H6
R
+
AlEt3
–C H6
2
3
Al
1
-alkyl-1-allylcyclopropanes 2 were identified by 1H
and 3C NMR and IR spectroscopy and mass spectrom-
1
Et
etry (Scheme 1).
ꢀ=a?
In the present work, this process was studied by
dynamic 13C NMR spectroscopy to reveal the mechanism
R
of the reactions of ACP with allyl halides in the presence
=
a?
of Ni(acac) and identify intermediate compounds.
2
R = n-C H9 (=); n-C H (>); n-C H (?)
4
6
13
9 19
Results and Discussion
The reactions were carried out in a glass reaction vessel
in a flow of an inert gas at ∼20 °C, with periodically
sampling for NMR analysis.
Alumacyclopentane 1 was mixed with allyl halide
and a catalytic amount of Ni(acac)2 in Et O at –5 °C.
2
The reaction of an ethereal solution of 1-ethyl-3-
(n-hexyl)alumacyclopentane (1b)3 with a threefold ex-
*
For Part 24 see Ref. 1.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1394—1397, August, 2001.
066-5285/01/5008-1465 $25.00 ©ꢀ2001 Plenum Publishing Corporation
1

1
466
Russ.Chem.Bull., Int.Ed., Vol. 50, No. 8, August, 2001
Dzhemilev et al.
Scheme 2
R
4
[Ni]
Cl
C H
1
Et Al
+
Et Al
Al
1´
+
–
R
3
6
Al
Al
H
H
Cl 1
1´
R
4
R
R
Cl
Et
ꢀ
=a?
!=a?
"=a?
#=a?
$=a?
+
H O
3
2
+
H O
Cl
3
1
+
R
Et Al
Cl
R
R
3
´
1´
R
R
&
=a?
%=a?
'=a?
ꢀꢁ=a?
ꢀꢀ=a?
R = n-C H9 (=); n-C H (>); n-C H (?)
4
6
13
9 19
cess of allyl chloride in the presence of freshly sublimed
mol. % Ni(acac) begins with the formation of unsat-
urated regioisomeric organoaluminum compounds (OAC)
tively (GLC data). This indicates the in situ formation
of intermediate regioisomeric OACs 5b, 6b, and 7b.
ACPs 1a and 1c react in a similar manner with allyl
chloride to give the corresponding unsaturated acyclic
OACs, which are transformed in situ (∼20 °C, 8 h,
5
2
5
b and 6b (Scheme 2).
The 13C NMR spectra of these compounds show
characteristic highfield signals from the α-carbon atoms
of OAC at δ 0.2—16.2, which are broadened owing to
Et O) into 1,1-substituted cyclopropanes 8a,c. The hy-
2
drolysis products contain, along with 1,1-disubstituted
cyclopropanes 8a,c, olefins 10a,c and 11a,c in the ratio
12 : 1 : 3, respectively (the total yield was ∼80%).
To find out how the structure of the starting allyl
halide influences the direction of cross-linking, the
catalytic transformations of ACP 1b in the presence of
crotyl bromide and methallyl chloride were studied
(Scheme 3). The reaction of OAC 1b with crotyl bro-
mide (Ni(acac)2 (5 mol. %), ether, 21—22 °C, 8-9 h)
gives regioisomeric cyclopropanes 12b and 13b (1 : 1) in
60% yield, suggesting the formation of the target prod-
ucts according to Scheme 2.
2
7
Al quadrupole relaxation (I
27Al
= 5/2). In addition,
their 13C NMR spectra contain signals at δ 155.1 and
07.1 from the doubly bonded C atoms in 5b and signals
1
at δ 148.2 and 111.5 from the vinyl group in 6b.
Apparently, low-valence Ni complexes initiate the
β-hydride transfer4 causing in situ reversible opening of
ACP 1b. The resulting regioisomeric aluminum hydrides
3
b and 4b reduce the starting allyl chloride to propy-
5
lene , irreversibly giving OACs 5b and 6b. Indeed, the
evolution of gaseous propylene was observed in these
experiments.
In the NMR spectrum recorded an hour after the
starting reagents (ACP, allyl chloride and Ni(acac)2)
Scheme 3
were mixed, the intensities of signals at δ 155.1 and
2
1
07.1 characteristic of the sp -hybridized carbon atoms
R
in OAC 5b noticeably decreased. After 24 h, the NMR
spectrum of this mixture does not virtually contain
resonance lines from the doubly bonded C atoms in 5b.
Hydrolysis of the mixture yields 1-(but-3-enyl)-1-
H C
Br, [Ni]
Cl, [Ni]
3
–
–
Al
Et
(
n-hexyl)cyclopropane (8b), probably, through intramo-
ꢀ
>
lecular cyclization of 5b into OAC 7b, which then
undergoes cross-linking with the starting allyl chloride
to give 8b in ∼65% yield (see Scheme 2). A minor
reaction product (∼20%) was identified as olefin 11b.
The study of the process dynamics showed that,
unlike OAC 5b, compound 6b is not involved in the
aforesaid transformation, being virtually unchanged
throughout the reaction time. Hydrolysis of the reaction
mixture (∼1 h after the reaction started) gives 1-(n-hexyl)-
6
2
1
2
6
1
1
+
+
2
2
R
R
R
3
´
1´
3´ 1´
1
R
">
ꢀ
>
ꢀ!>
ꢀ
ꢀ#>
R = n-C H
6
13
1
-methylcyclopropane (9b), 2-ethyloct-1-ene (10b), and
The reaction of ACP 1b with a threefold excess of
3
-methylnon-1-ene (11b) in the ratio 4 : 1 : 7, respec-
methallyl chloride in the presence of 5 mol. % Ni(acac)2

Conversion of alumacyclopentanes to cyclopropanes Russ.Chem.Bull., Int.Ed., Vol. 50, No. 8, August, 2001
1467
initially yields regioisomers 5b and 6b, which are in-
volved in situ in cross-linking with an excess of methallyl
chloride. The latter process occurs faster than intramo-
lecular carboalumination with the formation of cyclo-
propane-containing OACs of the type 7b. As the result,
a mixture of regioisomeric heptadienes 14b and 15b
with an IR-75 spectrometer (thin film). Mass spectra were
recorded on a Finnigan 4021 spectrometer (EI, 70 eV, ioniza-
tion chamber temperature 200 °C).
Synthesis of 1-alkyl-1-(but-3-enyl)cyclopropanes. Cp ZrCl
2
2
7
(
(
0.5 mmol) obtained according to the known procedure, α-olefin
10 mmol), and AlEt (12 mmol) were placed in a glass reaction
3
vessel in an atmosphere of dry Ar at 0 °C. The reaction mixture
was stirred at 21—23 °C for 8 h. To 3-alkyl-1-ethylalumacyclo-
pentane that formed3 Et O (8 mL), freshly sublimed Ni(acac)
(
1 : 1) is formed in ∼65% total yield.
The proposed method opens the route to the synthe-
2
2
sis of various 1,1-disubstituted cyclopropanes whose
structures are dependent on those of the starting α-olefins
and allyl halides. In particular, the cycloalumination of
(0.5 mmol), and allyl chloride (methallyl chloride or crotyl
bromide) (36 mmol) were added at –5 °C, and the resulting
mixture was stirred at ∼20 °C for 8—10 h. The course of the
1
13
process was monitored by dynamic H and C NMR spectros-
copy; samples (0.5 mL) were withdrawn at regular intervals.
After 8—10 h, the reaction mixture was hydrolyzed with 10% HCl
to give 1-alkyl-1-(but-3-enyl)cyclopropanes 8, 12, and 13. ACP
16 was obtained according to the known procedure6 from
2E,7-octadienol with a 2.5-fold excess of AlEt3 and a threefold
excess of allyl chloride with respect to AlEt.
2
E,7-octadienol under the action of AlEt3 in the
presence of 5 mol. % Cp ZrCl2 followed by the
2
6
Ni(acac) -catalyzed reaction of OAC 16 with allyl
2
chloride in Et O gives 1,1-disubstituted cyclopropane
2
1
7 in ∼50% yield (Scheme 4).
3
-Butylbut-3-enyl(ethyl)aluminum chloride (5a). 13C NMR,
Scheme 4
δ: 1.1 (br.t, C(1´)); 8.7 (q, C(2´)); 14.1 (q, C(4″)); 16.7 (br.t,
C(4)); 22.9 (t, C(3″)); 30.5 (t, C(2″)); 35.7 (t, C(1″)); 39.6
(
t, C(3)); 106.6 (t, C(1)); 154.5 (s, C(2)).
OH
Ethyl(3-hexylbut-3-enyl)aluminum chloride (5b). 13C NMR,
O
AlEt2
δ: 1.2 (br.t, C(1´)); 9.0 (q, C(2´)); 14.5 (q, C(6″)); 16.2 (br.t,
C(4)); 23.4 (t, C(5″)); 28.7 (t, C(2″)); 30.0 (t, C(3″)); 32.6
(t, C(4″)); 36.5 (t, C(1″)); 40.5 (t, C(3)); 107.1 (t, C(1));
155.1 (s, C(2)).
Ethyl(3-nonylbut-3-enyl)aluminum chloride (5c). 13C NMR,
δ: 1.5 (br.t, C(1´)); 8.8 (q, C(2´)); 14.3 (q, C(9″)); 16.8 (br.t,
C(4)); 23.1 (t, C(8″)); 28.3 (t, C(2″)); 28.4 (t, C(6″)); 29.8
(t, C(3″)); 29.9 (t, C(5″)); 30.1 (t, C(7″)); 32.4 (t, C(4″)); 36.1
[
Zr]
+
–C H
2
6
Al
AlEt3
Et
ꢀ
$
Cl, [Ni] –C H6
3
(
t, C(1″)); 40.1 (t, C(3)); 106.7 (t, C(1)); 154.6 (s, C(2)).
2-Butylbut-3-enyl(ethyl)aluminum chloride (6a). 1 C NMR,
3
2
1
4
´
δ: 1.1 (br.t, C(1´)); 8.7 (q, C(2´)); 14.1 (q, C(4″)); 16.7 (br.t,
C(4)); 23.1 (t, C(3″)); 29.0 (t, C(2″)); 31.7 (t, C(1″)); 41.4
(d, C(3)); 111.1 (t, C(1)); 147.7 (d, C(2)).
OH
3
″
1″ 1´
Ethyl(2-hexylbut-3-enyl)aluminum chloride (6b). 13C NMR,
δ: 1.2 (br.t, C(1´)); 9.0 (q, C(2´)); 14.5 (q, C(6″)); 16.2 (br.t,
C(4)); 23.4 (t, C(5″)); 28.4 (t, C(2″)); 30.3 (t, C(3″)); 32.1
ꢀ
%
Thus, the study of catalytic transformations of 3-alkyl-
-ethylalumacyclopentanes with allyl halides and the
1
(
t, C(4″)); 32.7 (t, C(1″)); 41.8 (t, C(3)); 111.5 (t, C(1));
identification of the reaction intermediates made it
possible to propose the most plausible mechanism for
the formation of 1,1-disubstituted cyclopropanes (through
intermediate acyclic unsaturated organoaluminum com-
pounds) and develop a preparative method for the syn-
thesis of cyclopropanes from 1-ethyl-3-alkylalumacyclo-
pentanes and allyl halides in the presence of Ni com-
plexes as catalysts.
148.2 (s, C(2)).
Ethyl(2-nonylbut-3-enyl)aluminum chloride (6c). 13C NMR,
δ: 1.5 (br.t, C(1´)); 8.8 (q, C(2´)); 14.3 (q, C(9″)); 16.8 (br.t,
C(4)); 23.1 (t, C(8″)); 28.1 (t, C(2″)); 29.9 (t, C(3″)); 29.9
(
t, C(6″)); 30.1 (t, C(5″)); 31.8 (t, C(7″)); 32.4 (both t, C(1″),
C(4″)); 41.5 (t, C(3)); 111.2 (t, C(1)); 147.8 (s, C(2)).
-(But-3-enyl)-1-butylcyclopropane (8a). B.p. 63—64 °C
1
22
–1
(
10 Torr), nD 1.4390. IR, ν/cm : 3085, 2970, 2935, 2870,
1645, 1470, 1390, 1025, 1010, 925. 1H NMR, δ: 0.22 (s, 4 H,
H(2), H(3), both ring); 0.89 (m, 3 H, Me); 1.20—1.39 (m, 4 H,
H(2″), H(3″)); 1.39—1.68 (m, 4 H, H(1´), H(1″)); 1.81—2.11
Experimental
m, 2 H, H(2´)); 4.68—5.70 (m, 3 H, H(3´), H(4´)). 1 C NMR,
3
(
δ: 12.1 (t, C(2)); 14.2 (q, C(4″)); 19.2 (s, C(1)); 23.1 (t, C(3″));
28.9 (t, C(2″)); 31.1 (t, C(2´)); 35.7 (both t, C(1´), C(1″));
113.8 (t, C(4´)); 139.4 (d, C(3´)). Found (%): C, 86.61;
H, 13.04. C11H20. Calculated (%): C, 86.76; H, 13.24.
Reactions with OAC were carried out in an atmosphere of
dry argon. Solvents were distilled over LiAlH4 immediately
before use. Commercially available 98% AlEt3 (Joint-Stock
Company "Nizhnekamskneftekhim") was used. The reaction
products were analyzed on a Chrom-5 chromatograph (flame
ionization detector, column 200 ½ 0.3 cm with 15% PEG-6000
or 5% SE-30 on Chromaton N-AW, 50—190 °C). 1H and
1-(But-3-enyl)-1-hexylcyclopropane (8b). B.p. 72—74 °C
2
2
–1
(5 Torr), nD 1.4445. IR, ν/cm : 3085, 2970, 2940, 2870,
1650, 1470, 1385, 1025, 1015, 925. 1H NMR, δ: 0.18 (s, 4 H,
H(2), H(3), both ring); 0.88 (m, 3 H, Me); 1.18—1.29 (m, 8 H,
H(2″), H(3″), H(4″), H(5″)); 1.40—1.65 (m, 4 H, H(1´),
H(1″)); 1.70—2.03 (m, 2 H, H(2´)); 4.52—5.55 (m, 3 H,
1
3
C NMR spectra were recorded on JEOL FX-90Q (90 and
2
2.5 MHz, respectively; with complete or partial proton
1
3
13
decoupling for C) and Bruker AM-300 spectrometers (300
and 75.46 MHz, respectively) with CDCl3 as the internal
H(3´), H(4´)). C NMR, δ: 12.1 (t, C(2)); 14.1 (q, C(6″));
19.2 (s, C(1)); 22.5 (t, C(5″)); 26.6 (t, C(2″)); 29.7 (t, C(3″));
31.1 (t, C(2´)); 32.0 (t, C(4″)); 35.6 (t, C(1´)); 36.0 (t, C(1″));
standard, except for OAC (C D12). IR spectra were obtained
6

1
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Russ.Chem.Bull., Int.Ed., Vol. 50, No. 8, August, 2001
Dzhemilev et al.
1
13.8 (t, C(4´)); 139.4 (d, C(3´)). Found (%): C, 86.48;
H, 13.24. C13H24. Calculated (%): C, 86.59; H, 13.41.
-(But-3-enyl)-1-nonylcyclopropane (8c). B.p. 88—90 °C
J = 6.1 Hz); 1.04—1.34 (m, 10 H, H(1´), H(2´), H(3´), H(4´),
H(5´)); 1.01 (s, 3 H, C(2)Me); 1.86—2.01 (m, 6 H, H(3),
H(4), H(5)); 4.40—5.67 (m, 4 H, H(1), H(7)). 13C NMR, δ:
14.2 (q, C(6´)); 21.1 (q, C(6)Me); 22.7 (t, C(5´)); 27.2 (t, C(4));
29.2 (t, C(3´)); 29.5 (t, C(2´)); 32.0 (t, C(4´)); 35.7 (t, C(1´));
36.2 (t, C(3)); 37.6 (t, C(5)); 108.7 (t, C(7)); 109.9 (t, C(1));
1
2
2
–1
(
1
2 Torr), nD 1.4499. IR, ν/cm : 3085, 2970, 2940, 2870,
650, 1470, 1385, 1025, 1010, 925. 1H NMR, δ: 0.21 (s, 4 H,
H(2), H(3), both ring); 0.88 (m, 3 H, Me); 1.15—1.30 (m,
+
1
1
4 H, H(2″), H(3″), H(4″), H(5″), H(6″), H(7″), H(8″));
.38—1.66 (m, 4 H, H(1´), H(1″)); 2.08—2.20 (m, 2 H,
146.0 (s, C(6)); 150.1 (s, C(2)). MS, m/z: 194 [M] . Found (%):
C, 86.21; H, 13.39. C14H26. Calculated (%): C, 86.52; H, 13.48.
1
3
H(2´)); 4.70—5.80 (m, 3 H, H(3´), H(4´)). C NMR, δ: 12.1
5-Hexyl-2-methylhepta-1,6-diene (15b). B.p. 79—81 °C
2
2
1
(
(
t, C(2)); 14.1 (q, C(9″)); 19.2 (s, C(1)); 22.8 (t, C(8″)); 26.6
t, C(2″)); 29.4 (t, C(6″)); 29.6 (t, C(3″)); 29.7 (both t, C(4″),
(2 Torr), nD 1.4422. H NMR, δ: 0.81 (t, 3 H, C(5´)Me,
J = 6.1 Hz); 1.04—1.34 (m, 12 H, H(4), H(1´), H(2´), H(3´),
H(4´), H(5´)); 1.86—1.93 (m, 2 H, C(3)); 1.93—2.10 (m, 1 H,
C(5)); 4.40—5.67 (m, 5 H, H(1), H(6), H(7)). 13C NMR, δ:
14.2 (q, C(6´)); 22.5 (q, C(6)Me); 22.7 (t, C(5´)); 29.6 (t, C(3´));
29.8 (t, C(2´)); 32.0 (t, C(4)); 33.0 (t, C(4´)); 35.2 (t, C(3));
35.5 (t, C(1´)); 43.9 (t, C(5)); 109.6 (t, C(1)); 114.4 (t, C(7));
C(5″)); 31.1 (t, C(2´)); 32.0 (t, C(7″)); 35.5 (t, C(1´)); 36.1
t, C(1″)); 113.9 (t, C(4´)); 139.4 (d, C(3´)). Found (%):
C, 86.15; H, 13.43. C16H30. Calculated (%): C, 86.41; H, 13.59.
-Hexyl-1-methylcyclopropane (9b). B.p. 80—83 °C (50 Torr),
(
1
nD22 1.4413. IR, ν/cm : 2905, 2970, 2872, 1460, 1380, 1010,
–1
25. 1H NMR, δ: 0.18 (s, 4 H, H(2), H(3), both ring); 0.86 (t,
H, C(5″)Me, J = 6.1 Hz); 0.92 (s, 3 H, C(1)Me); 1.20—1.53
143.4 (d, C(6)); 146.4 (s, C(2)). MS, m/z: 194 [M] . Found (%):
+
9
3
C, 86.32; H, 13.38. C14H26. Calculated (%): C, 86.52; H, 13.48.
1-(But-3-enyl)-1-(6-hydroxyhex-4-enyl)cyclopropane (17).
B.p. 120—123 °C (1 Torr), nD22 1.4902. IR, ν/cm–1: 3360,
3080, 3010, 2935, 2865, 1645, 1470, 1105, 1030, 985, 925.
1H NMR, δ: 0.24 (s, 4 H, H(2), H(3), both ring); 1.10—1.62
(m, 6 H, H(1´), H(2´), H(1″)); 1.84—2.20 (m, 4 H, H(3´),
H(2″)); 3.83 (s, 1 H, OH); 4.15 (d, 2 H, H(6´), J = 4.0 Hz);
(
m, 8 H, H(2″), H(3″), H(4″), H(5″)); 2.28 (t, 2 H, H(1″),
1
3
J = 6.6 Hz). C NMR, δ: 13.1 (t, C(2)); 14.2 (q, C(6″)); 15.5
(
(
s, C(1)); 22.8 (t, C(5″)); 27.0 (q, C(1´)); 29.6 (t, C(3″)); 29.8
t, C(2″)); 32.0 (t, C(4″)); 39.6 (t, C(1″)). Found (%): C, 85.35;
H, 14.28. C10H20. Calculated (%): C, 85.63; H, 14.37.
2
-Ethyloct-1-ene (10b). B.p. 82—84 °C (50 Torr),
nD22 1.4221. IR, ν/cm–1: 3080, 2960, 2950, 2930, 2880, 2855,
4.82—5.90 (m, 5 H, H(4´), H(5´), H(3″), H(4″)). C NMR, δ:
13
1
1
4
1
2
1
645, 1465, 1375, 890, 725. 1H NMR, δ: 0.89 (6 H, Me);
.20—1.64 (m, 8 H, H(4), H(5), H(6), H(7)); 1.90—2.28 (m,
H, H(3), H(1´)); 4.69—4.82 (m, 2 H, H(1)). 13C NMR, δ:
2.5 (q, C(2´)); 14.2 (q, C(8)); 22.8 (t, C(7)); 27.9 (t, C(4));
8.9 (t, C(5)); 29.2 (t, C(6)); 31.9 (t, C(1´)); 36.4 (t, C(3));
12.0 (t, C(2)); 19.0 (s, C(1)); 26.1 (t, C(2´)); 31.0 (t, C(2″));
32.4 (t, C(3´)); 35.5 (t, C(1´)); 35.5 (t, C(1″)); 63.8 (q, C(6));
113.9 (t, C(4″)); 129.0 (d, C(4´)); 133.6 (d, C(5´)); 139.3
(d, C(3″)). Found (%): C, 80.41; H, 11.53; O, 7.61. C14H24O.
Calculated (%): C, 80.36; H, 11.41; O, 8.23.
+
07.3 (t, C(1)); 152.0 (s, C(2)). MS, m/z: 140 [M] . Found (%):
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos. 00-15-
97312 and 01-03-32705).
C, 85.32; H, 14.28. C10H20. Calculated (%): C, 85.63; H, 14.37.
-Methylnon-1-ene (11b). B.p. 78—81 °C (50 Torr),
nD22 1.4223. IR, ν/cm–1: 3090, 2970, 2925, 2865, 1650, 1475,
385, 1010, 930, 740, 700. 1H NMR, δ: 0.86 (t, 3 H, C(8)Me,
J = 6.1 Hz); 0.98 (d, 3 H, C(3)Me, J = 4.2 Hz); 1.08—1.35 (m,
0 H, H(4), H(5), H(6), H(7), H(8)); 1.58—1.69 (m, 1 H,
3
1
References
1
H(3)); 4.92—5.01 (m, 2 H, H(1)); 5.44—5.88 (m, 1 H, H(2)).
1
2
. U. M. Dzhemilev, A. G. Ibragimov, I. R. Ramazanov, M. P.
Luk´yanova, and A. Z. Sharipova, Izv. Akad. Nauk, Ser.
Khim., 2001, 465 [Russ. Chem. Bull., Int. Ed., 2001, 50, 484].
. U. M. Dzhemilev, A. G. Ibragimov, A. P. Zolotarev, R. R.
Muslukhov, and G. A. Tolstikov, Izv. Akad. Nauk SSSR, Ser.
Khim., 1990, 1190 [Bull. Acad. Sci. USSR, Div. Chem. Sci.,
13C NMR, δ: 14.2 (q, C(9)); 20.3 (q, C(1´)); 22.8 (t, C(8));
2
(
7.4 (t, C(5)); 29.6 (t, C(6)); 32.0 (t, C(7)); 36.8 (t, C(4)); 37.9
d, C(3)); 112.3 (t, C(1)); 145.1 (d, C(2)). MS, m/z: 140 [M]+.
Found (%): C, 85.33; H, 14.29. C10H20. Calculated (%):
C, 85.63; H, 14.37.
1
-Hexyl-1-(trans-pent-3-enyl)cyclopropane (12b). B.p.
8—81 °C (2 Torr), nD22 1.4621. 1H NMR, δ: 0.04 (s, 4 H,
H(2), H(3), both ring); 0.84 (t, 3 H, C(5″)Me, J = 6.4 Hz);
.11—1.35 (m, 12 H, H(1´), H(1″), H(2″), H(3″), H(4″),
H(5″)); 1.74—2.02 (m, 2 H, H(2´)); 1.45—1.69 (m, 3 H,
1
990, 39, 1071 (Engl. Transl.)].
7
3. U. M. Dzhemilev, A. G. Ibragimov, and A. P. Zolotarev,
Izv. Akad. Nauk SSSR, Ser. Khim., 1989, 207 [Bull. Acad.
Sci. USSR, Div. Chem. Sci., 1989, 38, 194 (Engl. Transl.)].
1
4
. G. Henrici-Olivé and S. Olivé, Coordination and Catalysis,
Verlag-Chemie, Weinheim—New York, 1977.
1
3
C(4´)Me); 4.66—5.59 (m, 2 H, H(3″), H(4″)). C NMR, δ:
1
2
3
1
0.3 (t, C(2)); 14.2 (q, C(6″)); 17.9 (q, C(5´)); 18.6 (s, C(1));
2.8 (t, C(5″)); 25.8 (t, C(2´)); 28.0 (t, C(2″)); 29.6 (t, C(3″));
2.1 (t, C(4″)); 37.2 (t, C(1″)); 38.2 (t, C(1´)); 124.6 (d, C(4´));
5
. G. A. Tolstikov and V. P. Yur´ev, Alyuminiiorganicheskii
sintez [Organoaluminum Synthesis], Nauka, Moscow, 1979,
2
65 pp. (in Russian).
31.5 (d, C(3´)). Found (%): C, 86.21; H, 13.39. C14H26
.
6. U. M. Dzhemilev, A. G. Ibragimov, A. P. Zolotarev, and
Calculated (%): C, 86.52; H, 13.48.
-Hexyl-1-(2-methylbut-3-enyl)cyclopropane (13b). B.p.
3—75 °C (2 Torr), nD22 1.4541. 1H NMR, δ: 0.15 (s, 4 H,
H(2), H(3), both ring); 0.88—1.04 (m, 6 H, Me); 1.04—1.36
G. A. Tolstikov, Izv. Akad. Nauk SSSR, Ser. Khim., 1990,
1
2
831 [Bull. Acad. Sci. USSR, Div. Chem. Sci., 1990, 39, 2570
7
(Engl. Transl.)].
7
. A. N. Nesmeyanov, T. V. Nikitina, and O. V. Nogina,
Metody elementoorganicheskoi khimii. Kn. 1. Podgruppa medi,
skandiya, titana, vanadiya, khroma, margantsa. Lantanoidy i
aktinoidy [Methods of Organoelement chemistry. Vol. 1. Sub-
group of Copper, Scandium, Titanium, Vanadium, Chromium,
and Manganese. Lanthanides and Actinides], Nauka, Mos-
cow, 1974, 335 (in Russian).
(
(
m, 12 H, H(1´), H(1″), H(2″), H(3″), H(4″), H(5″)); 1.80—2.10
m, 1 H, H(2´)); 4.66—5.59 (m, 3 H, H(3´), H(4´)). 1 C NMR,
3
δ: 11.4 (t, C(2)); 14.2 (q, C(6″)); 19.3 (q, MeC(4´)); 19.7
(
(
(
s, C(1)); 22.8 (t, C(5″)); 28.5 (t, C(2″)); 29.2 (t, C(3″)); 32.1
t, C(4″)); 35.0 (t, C(2´)); 43.7 (t, C(1″)); 45.2 (t, C(1´)); 114.2
d, C(4´)); 143.3 (d, C(3´)). Found (%): C, 86.22; H, 13.40.
C14H26. Calculated (%): C, 86.52; H, 13.48.
-Hexyl-6-methylhepta-1,6-diene (14b). B.p. 99—101 °C
2
Received September 25, 2000;
in revised form May 10, 2001
2
2
1
(
5 Torr), nD 1.4421. H NMR, δ: 0.81 (t, 3 H, C(5´)Me,